Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
  • C09D5/12—Wash primers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/62—Alcohols or phenols
  • C08G59/621—Phenols
  • C08G59/623—Aminophenols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

• This invention relates to a water-borne cationic binder for wash primers, a method for its preparation, and a method of use thereof in corrosion protection of base metals.
• Aqueous wash primers based on externally emulsified polyvinyl butyral resin dispersions have been known, i. a., from EP 0 638 606 A .
• Such externally emulsified systems generally have the disadvantage that no direct pigmentation is possible due to the lack of shear stability of the emulsions so prepared.
• Anionically stabilised internally emulsified dispersions have shown enhanced stability, the corrosion protection imparted to base metals, however, has not been satisfactory.
• Cationically stabilised systems are preferable, as they allow the addition of phosphoric acid to improve the corrosion protection without gelation.
• a water-reducible polyvinyl butyral composition is prepared by reaction of an adduct of a diisocyanate and a tertiary alkanolamine with a polyvinyl butyral which, for statistical reasons, always possesses a number of free hydroxyl groups.
• This reaction product is then mixed with a water-compatible plasticising resin, such as an alkyd resin, a phenolic resin, and preferably, a phenoxy resin.
• a water-compatible plasticising resin such as an alkyd resin, a phenolic resin, and preferably, a phenoxy resin.
• the present invention is therefore related to a mixture AB comprising a mass fraction of from 5 % to 40 % of a polyvinyl butyral B , and a mass fraction of from 95 % to 60 % of a Mannich base A (wherein the mass fractions add to 100 %) made by a two-step reaction of an epoxy amine adduct A1 prepared in the first step from an epoxy resin A11 with a mixture A12 of a primary linear or branched aliphatic amine A121 having from 2 to 30 carbon atoms and a further aliphatic linear, branched or cyclic amine A122 having from 4 to 16 carbon atoms and having one primary and at least one tertiary amino group, which epoxy amine adduct A1 is reacted in the second step with formaldehyde and a phenolic compound A2 to form a Mannich base.
• This mixture AB is dispersed in water, after at least partial neutralisation of the amino groups by addition of an acid.
• a further object of the invention is a process for the preparation of the said mixture AB , comprising mixing the amines A121 and A122, preferably in an amount-of-substance ratio of n (A121) to n (A122) of from 0.5 mol : 2 mol to 2 mol : 0.5 mol, where n (X) is the amount of substance of compound X, X standing for either the amines A121 or the amines A122, reacting the said amine mixture A12 with an epoxy resin A11, where the amount of substance n (NH 2 ) of primary amino groups in the mixture A12 divided by the amount of substance n (EP) of epoxide groups in A11 is from 1.05 mol/mol to 1.3 mol/mol, to form the epoxy amine adduct A1, admixing the polyvinyl butyral B , adding to this mixture formaldehyde and a phenolic compound A2 , where the quantity employed of the said phenolic compound and that of formaldeh
• a further object of the present invention is a method of use of the mixture AB as binder in a wash primer which is applied to substrates of base metals to protect these from corrosive attack.
• wash primers are preferably made by first preparing a slurry of a pigment mixture preferably comprising inter alia, zinc phosphate and iron oxide, optionally adding fillers, preferably silicate based fillers such as talc or alumosilicates, wetting agents, dispersing agents, and thickeners, adding to this slurry the binder mixture AB , and homogenising the resulting mixture.
• the primer thus obtained is applied to a substrate by spraying or dipping, and dried.
• the epoxy resins A11 are preferably based on aromatic ethers of glycidyl alcohol, preferably of di- or polyvalent phenols such as bisphenol A, bisphenol F, dihydroxy diphenyl sulphone, and of novolaks, or esters of glycidyl alcohol and aromatic dihydric or polyhydric acids such as terephthalic acid. It is also possible to use these aromatic epoxy resins in mixture with aliphatic epoxy resins, preferably those derived from polyoxypropylene glycol which imparts improved elasticity to the binders. Especially preferred is the diglycidyl ether of bisphenol A.
• the amines A121 are preferably aliphatic amines having from four to twenty-four carbon atoms and one primary amino group, such as butylamine, hexylamine, 2-ethylhexylamine, decylamine, dodecylamine, tridecylamine, octadecylamine, and mixtures of aliphatic primary fatty amines made from fatty acids or fatty alcohols preferably obtained from natural sources. Particularly preferred are cocoalkyl amine, stearylamine, a commercially available mixture of C 16 - to C 22 -alkylamines, tallow amine, and oleylamine.
• the amines A122 having one primary and at least one tertiary amino group preferably have one dialkylamino group such as 3-N,N-dimethylaminopropylamine, 3-N,N-diethylaminopropylamine, N-(2-aminoethyl)-morpholine, N-(2-aminoethyl)-piperazine, and tris-(2-aminoethyl)amine.
• dialkylamino group such as 3-N,N-dimethylaminopropylamine, 3-N,N-diethylaminopropylamine, N-(2-aminoethyl)-morpholine, N-(2-aminoethyl)-piperazine, and tris-(2-aminoethyl)amine.
• the phenolic compounds A2 are preferably selected from the group consisting of monohydric mononuclear phenols, such as phenol itself, the isomers of cresol and xylenol, dihydric mononuclear phenols such as resorcinol, catechol, and hydroquinone, and their homologues such as 4-methyl catechol and 2-methylresorcinol, and particularly preferred, dinuclear dihydric phenols and derivatives of these such as bisphenol A, bisphenol F, dihydroxy diphenyl and dihydroxy diphenyl ether, dihydroxybenzophenone and dihydroxydiphenyl sulphone, as well the homologues thereof such as tetramethyl bisphenol A. Of these, bisphenol A is especially preferred.
• the polyvinyl butyral B has a viscosity of from 10 mPa ⁇ s to 1000 mPa ⁇ s (dissolved in ethanol, mass fraction of solids 10 %, measured according to DIN 53 015 at 23 °C), and a weight average molar mass, determined by size exclusion chromatography in tetrahydrofurane solution, as calibrated with polystyrene standards, of from 25 kg/mol to 500 kg/mol. Its mass fraction of vinyl alcohol moieties is typically from 9 % to 30 %.
• the amines A121 and A122 preferably mixed in an amount-of-substance ratio of n (A121) to n (A122) of from 0.7 mol: 1.8 mol to 1.8 mol: 0.7 mol, particularly preferred from 0.8 mol : 1.2 mol to 1.2 mol : 0.8 mol
• n (X) is the amount of substance of compound X
• the amino groups are neutralised with acid.
• the mass fraction of polyvinyl butyral in the mixture with the Mannich base is preferably from 7.5 % to 30 %, and particularly preferred from 10 % to 20 %.
• Admixing the polyvinyl butyral B to the newly formed epoxy amine adduct has been found preferable because of the favourable viscosity ratio of these two components while undiluted.
• aqueously dispersed binder mixture is then used to prepare a wash primer with the following general procedure:
• Deionised water is charged to a mixing vessel, additives such as wetting, thickening, and dispersing agents are optionally stirred in, and then, a mixture of pigments and fillers such as ferric oxide, zinc phosphate, alumosilicate, and talc, is added and homogenised in a bead mill or similar high efficiency mixing device.
• the binder solution is then added in the same mixer, where care is take that the temperature remains below 50 °C.
• a further thickening agent is added to adjust the viscosity and flow behaviour.
• the wash primer dispersion so obtained can be applied to a substrate by spraying, dipping etc. It has been found to be particularly effective for non-ferrous substrates such as aluminium, magnesium, zinc, zinc-coated steel, copper, brass, bronze, glass, and plastic substrates.
• SEC specific content of epoxide groups
• EP epoxide groups
• m B of component B in a solution or dispersion, of the mass of solids
• a mixture of 93 g of dimethylamino propylamine and 74 g of decylamine was charged in a vessel and heated to 50°C. Within one hour, 710 g of a xylene solution comprising a mass fraction of 75 % of a diglycidyl ether of bisphenol A having a specific content of epoxy groups of 2.083 mol/kg was added at this temperature under stirring, which stirring was continued for three further hours. The solvent was then removed by distillation under reduced pressure.
• a homogeneous mixture was prepared of 65 g of deionised water, 28 g of ®Additol VXW 6208 (commercial polymeric non-ionic dispersing agent, Cytec Surface Specialties Austria GmbH), 5 g of ®Surfynol SE-F (commercial nonionic wetting agent based on acetylenic diol, Air Products and Chemicals, Inc.), 86 g of ®Bayferrox 130 BM (commercial alpha-Fe 2 O 3 pigment, Lanxess Germany GmbH), 85 g of ®Heucopohos ZPO (commercial organically modified basic zinc orthophosphate hydrate, Heubach GmbH), 42 g of ®ASP 600 (hydrous aluminosilicate, Engelhard Corporation), 42 g of talc IT extra (Norwegian Talc AS), and 7 g of ®Acrysol RM-8W (hydrophobic modified ethylene oxide urethane rheology modifier, Rohm &
• a paint was obtained having the following characteristics: mass fraction of solids 51 % viscosity 200 mPa ⁇ s (measured at 23 °C and a shear gradient of 10000 s -1 ) m (pigment) / m (binder) 1 g/g pH 6.5 (measured in aqueous dilution, mass fraction of solids 10 %) Tack-Free Time 15 min m (X) stands for mass of component X
• 211 g (1.85 mol) of bisphenol A and
• reaction mixture was heated to from 150°C to 160 °C taking advantage of the exothermic reaction, which temperature was kept constant for about three to four hours.
• Full neutralisation of the basis nitrogen groups (amine number of 41 mg/g) yielded a stable dispersion having a mass fraction of solids of about 40 %, and a viscosity of about 50 mPa ⁇ s (measured according to DIN EN ISO 3219, at 23 °C).
• ®Mowital B 20 H were dissolved in 850 g of xylene and heated to 80 °C.
• 84 g of a solution were added very rapidly, comprising a mass fraction of 50 % of an isocyanate functional intermediate made from 174 g of toluylene diisocyanate and 89 g of dimethyl ethanolamine in xylene, as taught in Austrian Patent Specifications AT-B 342,169 , AT-B 346,989 , and AT-B 362,479 .
• the reaction mixture was kept at 100 °C for one hour until an amine number of 30 mg/g and a mass fraction of solids of 25 % were reached.
• 77 g of this dispersion were mixed with 7.6 g of a dispersing agent (®Additol VXW 6208, polymeric non-ionic dispersant, Cytec Surface Specialties Austria GmbH), 2.5 g of rheology additive (®Acrysol RM8W, solvent-free hydrophobically modified ethylene oxide urethane, Rohm & Haas Company), 7.7 g of fully deionised water, 3.8 g of ethylene glycol monobutyl ether, and 1.4 g of a defoamer (®Additol XW 376, aqueous emulsion of waxes and mineral oils, Cytec Surface Specialties Austria GmbH), to yield 100 g of a paste resin composition.
• a dispersing agent ®Additol VXW 6208, polymeric non-ionic dispersant, Cytec Surface Specialties Austria GmbH
• rheology additive ®Acrysol RM8W, solvent-free hydrophobically modified ethylene oxide urethan
• This paste resin composition was added to a pigment mixture comprising 11.5 g of ®Bayferrox 130 BM, 11.4 g of ®Heucophos ZPO, and 5.6 g each of ®ASP 600 and talc IT extra to yield 134.2 g of a pigment paste.
• wash primers were tested after application to a zinc-treated steel sheet (dry film thickness of 10 ⁇ m). The following results were found (GT0 for best, and GT5 for worst result in the cross cut test): Wash primer of Example 2 Comparative Wash primer of Example 3 Test Method Cross Cut Test 1 GT 0 GT 1 Water Resistance 2 72 h 24 h Corrosion Test 3 500 h 120 h Cross Cut Test 4 GT 0 GT 1 1 Performed on Wash Primer Layer on Metal Sheet 2 Wash Primer on Metal Sheet, Storage under Water at 23 °C, Time with no Visible Change of the Coating Layer 3 Salt Spray Test according to ASTM B 117 4 Performed on Additional Layer Made with a Water Based Top Coat

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
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• Wood Science & Technology (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Paints Or Removers (AREA)

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• 2006
  • 2006-03-01 EP EP06004139A patent/EP1829944A1/de not_active Withdrawn
• 2007
  • 2007-03-01 US US12/280,732 patent/US20090221465A1/en not_active Abandoned
  • 2007-03-01 EP EP07711736A patent/EP1989269A1/de not_active Withdrawn
  • 2007-03-01 WO PCT/EP2007/001762 patent/WO2007098947A1/en active Application Filing

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